US3757010A

US3757010A - Stilbene compounds

Info

Publication number: US3757010A
Application number: US00095935A
Authority: US
Inventors: H Balzer; F Fleck; H Schmid
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1969-12-11
Filing date: 1970-12-07
Publication date: 1973-09-04
Anticipated expiration: 1990-09-04
Also published as: ES386268A1; ZA708379B; DE2060085A1; NL7018032A; GB1299120A; JPS4924127B1; JPS527011B1; FR2073529A5; BE760178A; CH529770A

Abstract

EACH OF R3 AND R4 IS LOWER ALKYL OR LOWER HYDROXY ALKYL OR TOGETHER WITH N A SATURATED HETEROCYCLIC RADICAL, EACH OF R5 AND R6 IS H OR HAS THE MEANING OF R3 OR R4 R7 IS LOWER ALKYL BEARING OPTIONALLY-OH,-O-ALKYL, PHENOXY, CRESOXY OR PHENYL, ME IS E.G. NA, K, NH4+, ANION IS A COLOURLESS ANION, M IS 1 TO 3, N IS 1 OR 2, P IS 2 TO 6.

-CO-N(-R5)-R6

T AND Z EACH REPRESENTS THE RADICAL OF THE FORMULA II, R1 THE HYDROGEN OR LOWER ALKYL R2 IS-OH,-CN,-CO-CMH2M+1,

R1-CH(-R2)-(CH2)(N-1)-N(-)-CPH2P-N(-R3)-R4

X AND Y INDEPENDENTLY OF ONE ANOTHER EACH REPRESENTS AN OPTIONALLY SUBSTITUTED PHENYLAMINO RADICAL OR A RADICAL OF THE FORMULA

WHEREIN

YLENE)-Z

CH=CH-(2-(ME-O3S-)-1,4-PHENYLENE)-NH-(4-Y-2,6-S-TRIAZIN-

(2-T,4-X-S-TRIAZIN-6-YL)-NH-(3-(ME-O3S-)-1,4-PHENYLENE)-

STILBENE COMPOUNDS SUITABLE FOR THE BRIGHTENING OF TEXTILES IN COMBINATION WITH CATIONIC SOFTERNERS, OF PAPER AND OF WEAKLY ACIDIC SUBSTRATES. THEY HAVE THE FORMULA

Description

United States Patent 3,757,010 STILBENE COMPOUNDS Hans Balzer, Munchenstein, Basel-Land, Fritz Fleck, Bottmingen, Basel-Land, and Hans-Rudolf Schmid, Riehen, Basel, Switzerland, assignors to Sandoz Ltd. (also known as Sandoz AG), Basel, Switzerland No Drawing. Filed Dec. 7, 1970, Ser. No. 95,935 Claims priority, application Switzerland, Dec. 11, 1969, 18,425/ 69 Int. Cl. C07d 55/22 U.S. Cl. 260-240 B 17 Claims ABSTRACT OF THE DISCLOSURE Stilbene compounds suitable for the brightening of textiles in combination with cationic softeners, of paper and of weakly acidic substrates. They have the formula wherein X and Y independently of one another each represents an optionally substituted phenylamino radical or a radical of the formula T and Z each represents the radical of the Formula 11, R is hydrogen or lower alkyl R2 is OH, 'CN, COCmH2m+1,

It is generally known that textiles in domestic washing are treated in a rinsing bath following the actual washing operation with agents improving the handle of these textiles. Most of these agents for improving the handling properties (softeners) are cationic compounds.

In this way it is observed that those laundered goods which in the washing operation are brightened with anionic brighteners, such as those which are represented by way of example by bistriazinyl derivatives of 4,4-diaminostilbene-2,2'-disulphonic acid, suffer by the treatment with cationic softeners a more or less marked reduction in the degree of whiteness. However, this observation is made not only in the said case of household laundry, but every time when an anionic brightener and cationic softener are used simultaneously or in any desired sequence after one another for the treatment of textiles. However, it is not economical to use expensive washing agents containing anionic brighteners of a high quality for household laundry and to destroy by subsequent treat- 3,757,010 Patented Sept. 4, 1973 ment with cationic softeners the brightening efiect wholly or partly. Though the brightener itself is not destroyed in this way and is likewise not removed from the fibre, its fluorescence is appreciably weakened or completely obviated by the exchange etfect due to the cationic softeners.

It has now been found surprisingly that it is possible to obtain brighteners which, when used in the rinsing bath in very small amount together with the cationic softeners, are able to reinstate to the original value or to an even higher degree the whiteness degree reduced by the treatment with the softener, when there is introduced into the bistriazinyl derivatives of 4,4'-diaminostilbene-2, 2'-disulphonic acid 2 to 4 times, for example the residue of a 3-dialkylaminoalkylamine or of a 3-morpholinoalkylamine of which the amino radical contains in the l-position a substituted alkyl group and, optionally, the resulting products are quaternized. The new brighteners are differentiated from the ones known from Belgian patent specification No. 716,764 by an appreciably better drawing power on cellulose fibres in the cold in combination with cationic softeners.

The invention thus provides novel stilbene compounds of the formula N N t some SO Me N I x I Y wherein X and Y independently of one another each represents an optionally substituted phenylamino radical or a radical of the formula 1 zh-r T and Z each represents the radical of the Formula H or IH,

R represents hydrogen or a low molecular weight alkyl radical which may optionally be substituted with hydroxy, alkoxy, cyano, aminocarbonyl, phenyl, phenoxy or cresoxy radicals,

R represents hydrogen or a low molecular weight alkyl radical,

R represents hydroxy, a cyano, CO-C H or COOR radical,

R and R independently of one another each represents a low molecular alkyl or hydroxyalkyl radical or R and R together with the nitrogen atom represent a saturated heterocyclic radical,

R and R independently of one another each represents a hydrogen atom or a low molecular alkylor hydroxyalkyl radical or R and R together with the nitrogen atom represent a saturated heterocyclic radical,

R represents a low molecular alkyl radical which may optionally be substituted with hydroxy, alkoxy, phenoxy, cresoxy or phenyl,

Me represents an equivalent of an alkali or alkaline earth metal or ammonium radical,

Anion represents a colourless anion,

m represents a number from 1 to 3,

n represents 1 or 2 and 2 represents a number from 2 to 6,

(a) 1 mol of 4,4'-diaminostilbene-2,2'-disulphonic acid or a salt thereof, (b) 0 to 2 mols of an optionally substituted aminobenzene and (c) 2 to 4 mols of an amine of the formula or a mixture of amines of the Formula IV, with the proviso that the amines mentioned at (b) and (0) amount in all to 4 mols, and the reaction product is optionally reacted with an acid or a quaternizing agent, or that there are reacted in any desired sequence 1 mol of a cyanuric halide with (a) 1 mol of 4-amino-4'-nitroor -4'-acylaminostilbene- 2,2'-disulphonic acid or a salt thereof, (b) 0 to 1 mol of an optionally substituted aminobenzene and (c) 1 to 2 mols of amine of the Formula IV or of a mixture of amines of the Formula IV, with the proviso that the amines mentioned at (b) and (c) total 2 mols,

the nitro group is then reduced or the acylamino group hydrolysed and the amino group reacted with 1 mol of a cyanuric halide and the dihalogenotriazinyl compound is reacted in any desired sequence with (d) 0 to 1 mol of an optionally substituted aminobenzene and (e) 1 to 2 mols of an amine of the Formula IV or a mixture of amines of the Formula IV, with the proviso that the amines mentioned at (d) and (e) total 2 mols,

and the reaction product is optionally reacted with an acid or a quaternizing agent.

Examples of optionally substituted aminobenzenes are the following: aminobenzene and its deriati-ves which may contain in the 2-, 3- and/or 4-position low molecular weight alkylor alkoxy groups, halogen atoms, cyano groups, alkylsulphonyl groups, optionally monoor disubstituted sulphonic acid amide groups or acylamino groups, for example 2-, 3- or 4-methyl, 2,4, 2,5-, 2,6- or 3,5- dimethyl-, 2,4,6- or 2,4,5-trimethyl l aminobenzene, 4-ethyl-, 4-iso-propyl-, 4-n-propyl-, 4-n-butyl, 4-tert.- butyl-, 4-n-amyl-l-amino benzene, 2-, 3- or 4-chlor0-laminobenzene, 2,4- or 2,5-dichloro- 1 -aminobenzene, 4- fluoroor 4-bromo 1-aminobenzene, 4-cyan0-, 4-methylsulphonylor 4-ethylsulphonyl-l-aminobenzene, 3- or 4-aminosulphonyl-, 3- or 4-methylaminosulphonyl-, 3- or 4-ethylaminosulphonyl-, 3- or 4-dimethylaminosulphonyL, 3- or 4-(2'-hydroxyethylaminosulphonyl)-, 3- or 4-(2- or 3'-hydroxpropylaminosulphonyl)-, 3- or 4-di-(2'-hydroxyethyl)-aminosulphonylor 3- or 4-morpholinosulphonyl-l-arninobenzene.

Examples of acylamino groups optionally substituted are benzoylamino-, phenylsulphonylamino-, alkylsulphonylaminoand especially the alkanoylaminoand alkoxycarbonylamino groups, for example benzoylamino, 4-methylor 4-chlorobenzo'ylamino, phenyland 4-methylphenylsulphonylamino, methyl-, ethyland n-propylsulphonylamino, propionylamino, butyrylamino, acetylamino, methoxycarbonylamino, ethoxycarbonylamino.

Suitable aminobenzenes with such substituents are, for example, 4 propionylamino-, 4-acetylamino-, 3-acetylamino-, 4-methoxycarbonylaminoor 4-ethoxycarbonylamino-l-aminobenzene.

The aminobenzenes may also be substituted at the nitrogen atom, for example, as in the following compounds: N-methyl-, N-ethylor N-2-hydroxyethylaminobenzene, 3-methyl-l-N-methylor -N-ethylaminobenzene.

Am inobenzenes which are preferably used are: aminobenzene, l-amino-2-, -3- or -4-methylor -chlorobenzene, 1-amino-2- or -4-methoxyor -ethoxybenzene.

The radical A is a low molecular weight alkyl radical which contains the substituent designated as R for example 2-hydroxyethyl, 2-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 2-oxopropyl, 2-oxobutyl, 3-oxobutyl, aminocarbonylmeth'yl, Z-aminocarbonylethyl, 2-dimethylaminocarbonylethyl, 2 diethylaminocarbonylethyl, Z-moropholinocarbonylethyl, 2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2 n butoxycarbonylethyl, 2-(2'-hydrox'yethoxycarbonyl)-ethyl, 2 (2'-hydroxyprop0xycarbonyl)-ethyl, 2-(3'-hydroxypropoxycarbonyl)-ethyl, 2-(2'- methoxyethoxycarbonyl)-ethyl, 2 (2-ethoxyethoxycarbonyl)-ethyl, 2-(2'-n-butoxyethoxycarbonyl)-ethyl, 2-benzyloxycarbonylethyl and 2- (2'-pheny1ethoxycarbonyl)- ethyl.

The radical of the amine of the Formula IV is exemplified by 2-dimethylamino-, 2-diethylamino-, Z-N-methyl N ethylamino-, 2 di n butylamino-, 2-di-(2-hydroxyethyl)- amino, Z-N-methyl N (2'-hydroxyethyl)-amino-, 2-N- ethyl N (2'-hydroxyethyl)-amino-, 2-m0rph0lin0- or 2-piperidino-eth'ylamino, 3-di-ethylamino-propyl-Z-amino, 3-dimethylamino-, 3-diethylamino-, 3-N-methyl-N-ethylamino-, 3 N methyl-N-n-propylamino-, 3-N-ethyl-N-nbutylamino-, 3 di n propylamino-, 3-di-n-butylamino-, 3-di-n-pentylamino-, 3-di-(2-hydroxyethyl)-amino-, 3-N- methyl-N4 2'-hydroxyethyl -amino-, 3-N-ethyl-N- (2-hydroxyethyl)-amino-, 3-morpholino-, 3-pyrrolidino-, 3-piperidinoor 3-hexamethyleneimino-propylamino, 4-dimethylamino-, 4-diethylamino-, 4-N-methyl N ethylamino-, 4-di-n-butylamino-, 4-N-ethyl N (2-hydroxyethy1)-amino-, 4-di-(2'-hydroxyethyl)-aminoor 4-mlorpholinobutylarnino, 5-diethylamino-, S-di-n-butylaminoor S-N-methyl N ethylamino-pentylamino, 6-dviet-hylamino-, 6-di-n-butylamino- 0r 6-N-methyl-N-ethylaminohexylamino.

Preferred amines of the Formula IV are, for example, N- (3-dimethylaminopropyl N- 3-diethylaminopropyl N- 3-di-n-butylaminopropyl) N- 3-morpholinopropyl) N-( S-piperidino-propyl) N- 3-N'-ethyl-N'-methylaminopropyl)-N-aminocarbonylmethyl-amine, -N-(2'-cyanoethyl)-amine, -N-(2-aminocarbonylethyl)-amine, -N-(2'-dimethylaminocarbonylethyl)-amine, -N-(2'-diethylaminocarbonylethyl)-amine, -N-(2-morpholinocarbonylethyl)- amine, -N-(2-ethoxycarbonylethyl)-amine, -N-(2'-methoxycarbonylethyl)-amine, -N-(2 hydroxyethoxycarbonylethyl -amine, -N- 2'-methoxyethoxycarbonylethyl amine, -N-(2'-methylcarbonylethyl)-amine, N-[3-di-(2'- hydroxyethyl)-aminopropyl N (2"-cyanoethyl)-amine, -N(2"-aminocarbonylethyl) amine, -N-(2"-dimethylaminocarbonylethyl) amine, -N-(2 diethylaminocarbonylethyl) amine, -N-(2"-morpholinocarbonylethyl)- amine, -N-(2"-ethoxycarbonylethyl)-amine, -N-(2"-hydroxyethoxycarbonylethyl) amine, -N-(2"-methoxyethoxycarbonylethyl) -amine, -N- (2"-methylcarbonylethyl amine.

T'he amines of the Formula 'IV required as intermediate products may be obtained, for example, by the reaction of amines of the formula with acrylonitrile, optionally substituted acrylic acid alk'yl esters and acrylic acid amides or with the corresponding methacrylic acid derivatives, with alkylene oxides (especially ethyleneand propylene oxide) or with vinyl-alkyl tketones (vinyl-methyl ketone), at temperatures of from -100 C. (20-60).

Suitable quaternizing agents are for example, esters of sulphuric acid, e.g. dimethylsulphate or diethylsulphate, or the esters of aromatic or aliphatic sulphonic acids, e.g. benzene-, 4-methylbenzeneor 4-chlorobenzenesulphonic acid methyl ester, -ethyl ester or n-but'yl ester, methane-, ethane-, l-propaneor 2-propanesulphonic acid methyl ester or -ethyl ester. As alkylating agents there are suitable also alkyland aralkylhalides, e.g. methylchloride, methylbromide, ethylbromide, n-butylbromide, benzylchloride and benzylbromide. Furthermore, there may be used as alkylating agent alkylhalides with from 1 to 5 carbon atoms which are substituted with hydroxyl, alkoxy, phenoxy, cresoxy, cyano or preferably with aminocarbonyl groups, e.g. 2-chloroor 2-bromoethano1, 2-methoxy-, 2-ethoxy-, 2-n butoxy-, Z-phenoxyor Z-paracresoxyethyl chloride or bromide, chloroacetonitrile and preferably chloroor bromoactic acid amide or fi-chloropropionic acid amide.

The reaction with cyanuric halides, e.g. cyanuric bromide and especially cyanuric chloride, with the 4,4'-diaminostilbene-2,2'-disulphonic acid or with a water soluble salt thereof is effected with aqueous medium when the cyanuric halide is merely suspended in water, or in aqueous-organic medium when the cyanuric halide is first dissolved in an organic solvent (benzene, toluene, chlorobenzene, acetone) and the solution is added dropwise to an aqueous solution of the 4,4'-diaminostilbene-2,2'-disulphonic acid. The addition of a dispersing agent may increase the reaction velocity.

The replacement of the first halogen atom of the cyanuric halide is carried out at temperatures of from 0 to C. and pH values of from 3 to 7. The replacement of the second halogen atom [introduction of an optionally substituted phenylamino residue or of a residue of the Formula II] is suitably effected in the temperature range of from to 60 C. and at a weakly acid to weakly alkaline reaction, for example at pH values of from 4 to 8, while for the replacement of the third halogen atom [introduction of a residue of the Formula II] the temperature is advantageously kept to 80 to 100 C. and the pH value between 4 and 10.

The hydrogen halide liberated during the reaction is neutralized with alkalis, for example an alkali metal hydroxide or carbonate, or tertiary organic amines, e.g. triethanolarnine.

The isolation of the unquaternized brightener produced according to the invention may be effected by salting out, acidifying or evaporating the reaction solution, whereby pulverulent products result. However, it is likewise possible, after separating the salts, to produce liquid products with the addition of a solubilizing agent, such as for example a polyvalent alcohol [ethyleneor propylene glycol, dior tri-ethylene glycol, polyethylene glycol, dior tri-propylene glycol, 1,3-dihydroxypropane, 1,4dihydroxybutane, 2,3-dihydroxybutane, 2-methy1 2,4 dihydroxypentane, glycerine, hexanetriol, bis-(2'-hydroxyethyl)-sulphide], ether alcohol [2-methoxy-, 2-ethoxyor 2-n-butoxy-ethanol, 2-(2'-ethoxy-ethoxy)-ethanol, 2-(2- n-butoxyethoxy)-ethanol], a sulphoxide or sulphone (dimeth'ylsulphoxide, di-ethylsulphoxide, tetramethylenesulphone), an amide [formamide, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, phosphoric acid-tris-(dimethylamide), urea] or an alkanolamine (mono-, dior tri-ethanolamine or -propanolamine).

The quaternization may be effected in aqueous, aqueous-organic or organic suspension or solution at temperatures of from 0 to 100 C. and pH values of from 4 to 8, preferably at 20-60 C. and in the pH range of from 6 to 8. All tertiary amino groups or only some of them may be quaternized, at least 1 mol of the quaternizing agent being used for each tertiary amino group to be quaternized. When using a volatile quaternization agent, e.g. methylchloride, methylbromide, ethylbrornide, it is suitable to work in a pressurized vessel. Any excess of quarternizating agent is destroyed by the addition of sodium hydroxide solution and stirring the mixture at about 60 C. until the pH value no longer changes. The above mentioned polyvalent alcohols, ether alcohols, sulphoxides, sulphones and amides or their mixtures with water are suitable reaction media for the quaternization.

In order to obtain the compounds of the Formula I in which R [Formula III] represents hydrogen, the compounds with tertiary amino groups are stirred in water or a mixture of water and a solvent mentioned for the quaternization of 1 mol of acid is added for each tertiary amino group to be protonized. Working is advantageously effected at 0 to 100 C., preferably at 20 to C., in such a way that all tertiary amino groups present are protonized and the pH value of the solution or suspension is adjusted to about 3 to 5. As acids there may be used strong inorganic acids, e.g. hydrogen chloride or hydrogen bromide; however, organic acids, e.g. formic acid, acetic acid, propionic acid or oxalic acids, are likewise suitable.

The isolation of the protonized or quaternized compounds may be effected in the above described manner.

Valuable brighteners correspond to the formula X and Y independently of one another each represents a phenylaminoor methylphenylamino radical or a radical of the formula (VII) T and Z each represents a radical of the Formula VII or of the Formula VIII and Me, R, R R and R have the above significance.

Particularly valuable brighteners are those of Formula VI, wherein R [in the Formulae VII and VIII] represents an optionally monoor disubstituted aminocarbonyl radical.

The new brighteners produced according to the invention are suitable in the non-quaternized form and especially in the quaternized form for the brightening of textiles in combination with cationic softeners which may optionally also contain antistatically effective agents. Thanks to their excellent drawing ability on to cellulose fibres in the cold in the presence of cationic softeners they are especially suitable for use in soft rinsing agents which have been used in households for some time.

The quantities of brightener to be used amounts to |1-10% preferably 36%, based on 100% softener.

The brighteners of the invention afford the possibility to industry to combine simply and economically brightening and improvement of handle. Furthermore, they improve the appearance of weakly acid substrates, preferably of inorganic nature, e.g. silica, clay, kaolin etc, which is of especial importance in the paper industry.

A likewise very good brightening effect is shown by the brighteners according to the invention when used as coating compositions for papers.

Those of the brighteners according to the invention which contain 4 quaternized amino groups may likewise be applied to cellulose fibres from strongly acid medium, for example at pH values of from 1 to2, and show good brightening effects. They may be used together with auxiliaries for crease-proofing cellulose fibres, for example with resins such as dimethylolethylene urea, dimethylolpropylene urea, dimethylol-4,5-dihydroxyethylene urea, dimethylolmonoalkyl-carbamate and others. The condensation of synthetic resins is effected in a pH value range of from 1 to 2 which is usual in moist or wet cross-linking.

In the following examples parts and percentages are by Weight and tempenatures are stated in degrees centignade.

EXAMPLE 1 A solution of 190 parts cyanuric chloride in 635 parts acetone is run into 2000 parts of ice water during 10 minutes. A solution of 185 parts of 4,4'-diaminostilbene- 2,2'-disulphonic acid and 106 parts of anhydrous sodium carbonate in 1500 parts of water is then added dropwise at to 5 while stirring during one hour into the resulting suspension. In this way a suspension results which contains 355 parts of the sodium salt of 4,4'-bis-(2",4"-dichloro-1",3",5"-triazinyl-6"-amino) stilbene 2,2-disulphonic acid. After the diazo reaction no longer shows primary, aromatic amino groups, 93 parts of aminobenzene are added to this suspension, the mixture is heated to 40 for one hour while gradually adding 400 parts of sodium hydroxide solution, 201 parts of 3-(3'-diethylaminopropylamino)-propionic acid amide are added, and, after distilling off the acetone, the mixture is heated for 5 hours to 95-100 while gradually adding a further 400 parts of 10% sodium hydroxide solution. The product which separates out in the warmth as a viscous mass, becomes solid aud brittle on cooling. After separating off the mother liquor, the product is comminuted, stirred with 1500 parts of cold water, suctioned off and dried in a vacuum. It is highly suitable for brightening textilt s of all kinds, especially those from cotton in the cold in the presence of cationic softeners such as for example distearyldimethylammonium chloride.

The resulting brightener corresponds to the formula The required propionic acid amide is produced by adding 71 parts of acrylic amide to parts of B-diethylaminopropylamine at 40 and continuing stirring for one hour at this temperature.

EXAMPLE 2 To the suspension, obtained according to Example 1 of 355 parts of the sodium salt of 4,4'-bis-(2",4"-dichloro- 1",3",5-triazinyl 6" amino) stilbene-2,2'-disulphonic acid in 2000 parts of water and 635 parts of acetone there is added, while stirring, at 12 during about 10 minutes 201 parts of B-(3'-diethylaminopropylamino) propionic acid amide, the mixture is heated, while gradually adding 400 parts of 10% sodium hydroxide solution, to about 40 and stirring for one hour at this temperature is effected, a further 201 parts of the same propionic acid amide are added and the mixture, after distilling off the acetone, is heated for 6 hours to 95-100 while gradually adding 400 parts of 10% sodium hydroxide solution. The product is separated out in the warmth in the form of a viscous mass and is completely separated by the addition of sodium chloride g./ litre). The brightener is suctioned off, washed with dilute sodium chloride solution and dried. It constitutes a light yellow powder which is very effective, in combination with cationic softeners, for brightening cotton and alone for brightening weakly acid substrates, e.g. silica, clay or kaolin.

The brightener produced as above corresponds to the formula H H; HEN-m0 JH,-N o,H

An equally effective brightener is obtained when in this example the 18-(3'-diethylaminopropylamino) propionic acid amide is replaced once or twice each with 233 parts of fl-[3'-di-(2" hydroxyethyl) aminopropylaminoJ- propionic acid amide or each with 257 parts of [3-[3'-di- (n-butyl)-+aminopropylamino]-propionic acid iamide, the procedure being otherwise the same. These amines are produced, for example, by the reaction of 3-[di-(2'-hydroxyethyl)-amino]-propylamine or of B-di-n-butylaminopropylamine with acrylic acid amide in the manner described in Example 1.

EXAMPLE 3 To the suspension, obtained according to Example 1, of the sodium salt of 355 parts of 4,4'-bis-(2,4"-di chloro-1",3,5-triazinyl 6" amino)+stilbene-2,2'-di sulphonic acid in a mixture of acetone and water there is added, while stirring at 12, first 46.5 parts of aminobenzene and the temperature is allowed to rise slowly while simultaneously adding dropwise 10% sodium hydroxide solution. After about 15 minutes the diazo reaction no longer shows the presence of aminobenzene. While simultaneously introducing dropwise sodium hydroxide solution, 53.5 parts of 1-amino-2-methylbenzene are added subsequently. In all 400 parts of 10% sodium hydroxide solution are added dropwise and the temperature at the end has been increased to 40. At this temperature the mixture is stirred for one more hour and then 201 parts of {3-(3 diethylaminopropylamino) propionic acid amide are added. The resulting mixture is heated for 4 hours to 95-100 while slowly adding 400 parts of 10% sodium hydroxide solution. The product is completely separated by the addition of sodium chloride (100 g./litre), after cooling it is comminuted, filtered off and washed with 10% sodium chloride solution and dried in a vacuum.

The resulting product contains as active component a compound of the formula 5 eners as are the products described in Examples 1 to 3.

When the aminobenzene and the 1-amino-2-methylbenzene used in this example are together replaced with 215 parts of fi-(3-morpholinopropylamino)-propionic acid amide, a product results which is very similar in effect to compound first mentioned in Example 2.

EXAMPLE 5 A solution of 19 parts of cyanuric chloride in 100 parts of acetone is run into 200 parts of a mixture consisting of equal parts of ice and water. A solution, neutralized with sodium hydroxide, of parts of 4nitro-4'-aminostilbene- 2,2'-disulphonic acid in 400 parts of water is added drop- I HgN-O C-C Hz-CHr-N in addition to small quantities of the symmetric compounds containing two phenylamino residues or two 2- methylphenylamino residues and is as elfective as the symmetrically substituted brightener described in Example 1.

EXAMPLE 4 To the suspension, produced'as in Example 1, of 355 parts of intermediate product from cyanuric halide and 4,4-diaminostilbene-2,2-disulphonic acid in a mixture of acetone and water there are added first, while stirring at 10-12", 46.5 parts of aminobenzene and then 53.5 parts of 1-amino-2-methylbenzene, the procedure being as in Example 3. After the presence of the aromatic primary amines is no longer detectable, 215 parts of ;S-(3'-morpholinopropylamino)-propionic acid amide are added at 40 to the suspension and the mixture is heated for 5 hours to -400 while simultaneously adding dropwise 400 parts of 10% sodium hydroxide solution. The product is completely separated ofi by salting out g. of sodium chloride/litre) and worked up in the usual way.

The brightener present in the form of a yellow powder contains mainly the compound of the formula SOaNa S OaNa SOaNB wise during 10 minutes at 0-5 while stirring to the resulting suspension. During the course of one hour a solution 35 of 5.5 parts of sodium carbonate in 50 parts of water is added dropwise in such a way that the reaction product is always weakly acid to neutral (pH value 6 to 7). To the mixture which has been neutralized and freed from starting material, there are then added 9.3 parts of aminobenzene, the temperature is raised during about one hour to 35 and stirring is continued at this temperature until aminobenzene can no longer be detected with the diazo test, which occurs after 1-2 hours. The resulting hydro- 45 chloric acid is neutralized by the gradual addition of a 0 hours is continued at this temperature, whereby the resulting hydrochloric acid is continuously neutralized with O N CH=C C I-CHz-CH -CO-NH,

LH CHrCH N C 2 5) 1 1 1 2 is separated after cooling by the addition of sodium This stilbene compound is slightly more effective than the chloride, filtered off and washed with 10% sodium chlonon-quaternized compound of the Formula IX for ride solution. brightening cotton in combination with cationic softeners. The p after it has n w h n r l, is h n Instead of dirnethylsulphate it is possible to use 15.4 added during the course of one hour at 90100 in a mix- 5 parts of diethylsulphate or 18.6 parts of 4-methylbenture consisting of 500 parts of water, 66 parts of iron zenesulphonic acid methyl ester for effecting quaternizafilings and 15 parts of glacial acetic acid. As soon as nitro tion. When benzylc'hloride is used as quaternization agent compound has disappeared, the solution is made alkaline (12.65 parts), advantageously working is effected at room with sodium carbonate, filtered and the resulting solution temperature (about 24 hours).

of the disodium salt of 4-amino-4'-[2-phenylamino-4"- 4"-N-(2"'aminocarbonylethyl)-N (3"" diethylamino- EXAMPLE 7 propyl) amino 1",3,5" triazinyl 6" amino] -stil- Working is effected in the manner described in Ex bene-2,2'-disulphonic acid has its pH value adjusted to 7 ample 6 'While using 68.4 parts mol) of the comby adding dilute hydrochloric acid. This solution is added pound of the Formula X or 79.5 parts 1 mol) of the dropwise during 10 minutes at 010 to a suspension compound bearing di-(n-butyD-amino groups instead of which has been obtained by mixing 19 parts of cyanuric the di-ethylamino groups (last paragraph of Example 2) chloride, dissolved in 100 parts of acetone, with 100 parts and 25.2 parts of dimethylsulphate and quadruple of ice and 100 parts of water. The resulting hydrochloric quaternized compounds result.

acid is again neutralized by gradually adding a solution of 5.5 parts of sodium carbonate in 50 parts of water. When 20 EXAMPLE 8 the condensation is complete, 10.7 parts of 1-amino-2- Parts /20 11101) of the e p 0t Foflllllla IX methylbenzene are added, the temperature is raised during are StllTed at room temperature In 550 Parts Of nn ylone hour to 30 and stirring at this temperature is conformamide and dissolution is elfected by the addition of tinued for 4 hours, whereby the resulting hydrochloric 30 Parts Of Water- During about 15 minutes Parts Of acid is neutralized by gradually adding sodium carbonate 85% formic acid are added dropwise to this Solution, solution. 20,1 parts of l3-(3'-diethylaminopropylamino)- whereby the pH value drops (0 4 t0 5. A stable solution propionic acid amides are then added to the reaction mixo t e protoni d brightener results.

ture, the temperature is raised to 85 and stirring at this temperature for 4 hours is effected, while simultaneously EXAMPLE 9 neutralizing the resulting hydrochloric acid with sodium 74.8 parts & mol) of the brightener of the formula JH, 011L011 carbonate as already described. After the addition of so- (produced according to the last paragraph of Example 2) dium chloride, cooling to room temperature is efiected. are dissolved at 60 7 i 330 a t of dimethylfor- This product separates out in the warmth as a viscous 7 mass which solidifies on cooling. It is then pulverized, amlde and 330 parts of water Whlle Surfing About 24 washed with sodium chloride solution and dried in a Parts of 30% hydrochloric acid are then added so as vacuum. A yellowish powder results which is practically to adjust the pH value to about 3 to 4, and a stable soluinsoluble in Water, but is easily Soluble in dimethylfof'mtion results of the protonized brightener in the form amide or dimethylsulphoxide. It corresponds to the Forof the hydrochloride mula XI. The product is ettective as a brightener in manner similar to the product obtained according to Exam- By replacmg the bnghtener of Formula XV by the l 3 EXAMPLE 6 I other brightener described in the last paragraph of Ex- 57'6 parts of 2420 of the compound of the ample 2 which contains dI-(n-butyD-aminO groups inmula IX are stirred into 547 parts of dirnethylformamide stead of d1(fl'hydroxyethyn'ammo groups a snmlafly at room temperature and a clear solution is produced by protonized brightener is Producedadding 29 parts of water. During about 30 minutes 12.6 Th f ll i T bl 1 contains f h Symmetric parts of dimethylsulphate are added dropwise to this stilbene compounds of the Formula I which are solution, stirrmg is then effected for 2 hours at room temperature and during one hours at 00 Any Small excess of duced according to the details 1n Examples 1 and 2 and dimethylsulphate is destroyed by the addition of sodium 60 are Characterized y the Symbols X, Z and hydroxide solution while stirring at 60. The reaction solution contains, in addition to small amounts of un- TABLE 1 quaternized compound of the Formula IX, the compound Em of the formula No. X=Y T=Z Me '1 10- 2-methylphenylamino Ni (I2(-3a z n(iir1oe}ar}Jonyl-ethyl)- Na 'et y amino- NH HN propyD-amino.

N 11-... 4-methylphenylarmno do Na so 9 12 3-chlorophenylamino do Na 3 13. Z-methoxyphenylamino do N H4 I g.... 4-ethgxlyphenylfiminlo go--- g 4-ace yaminop enyo a N CH; CH OO NH, aminm Hm 02H 16. 3-methylphe11ylemino..-.. N-(2'-aminocarbonylethyl)- Na N -(3 isiimethylaminopropy amino.

CH3 g 17 4-chlorophenylamino. .d

C2135 2 18. 4-methoxyphenylarninm (XVI 19.--- 2,4-dimethylphenylamino TABLE 2 Ex. X Y T Z Me No.

90 Phenylamino 2-methylphenylamino N-(2-aminoearb0nylethyl)-N-(3- N-(2-aminocarbony1ethyl)-N-(3- Na dimethylaminopropyl) amino. dimethylaminopropyl) amino. 91 ..do do do N-(2-aminocarbonylethyl)-N-(3- Na diethylaminopropyl)-amjno. 92 do 4-methylphenylamino N-(2-aminoearbonylethyl)-N-[3-di- -..d Na

(n-butyl) -aminorpopyl]-aminot 93 -.do 4-ehlorophenylamino N-(2-cyanoethyl)-N=(3-diethyl- .d0 Na amino-pr0pyl)-amin0. 94 .do Z-methylphenylamino N-aminocarbonylmethyl-N-(3-diethyl-aminopropyD-amino. 95 do 4-methoxyphonylamino N-(2-aminocarbonylethyl)-N-(3- diethylaminopropyl)-amino. 96 Z-methyl-phenylamino. 4-methylphenylamino N-oyanomethyl-N-(3-diethylamino- N-(2-aminoearbonylethy1)-N-(3- Na propyD-amino. morpholinopl'opyl)-amin0. 97 2-methylphenylamino Phenylamino N-(2-aminocarbonylethyl)-N-[3-di- N-(2-aminoearbonylethyl)-N-(3- Na (B-hydroxyethyl)aminopl'opylI- morpholinopropyl)-amin0. ammo. 98 3-rnethy1phenylamino do do N-(2-arninoearbonylethyl)-N-[3"-di- Na s-hydroxyethyl)-an1inopropyl]- annno. 99 4-ethoxyphenylamino do do Na 100.-.. Phenylarnino dn dn carbonylethyl)-N-(3- Na piperidin0pr0pyl)-amino. 101 do do dn N-(2-amin0earbonylethyl)-N-(2- Na diethylaminoethyl)amino. 102 do 2-methy1phenylamino N-(2-hydroxyethyl)-N-(3-diethyl- N-(2-hydr0xyethyl)N-(3-d.iethyl- Na aminopropyyD-amino. aminopropyD-amino. 102 dn do N-(2aminoearbonylethyl)-N-(3- N-(2-ethoxyearbonylethyl)-N-(3- Na diethylaminopropyl)-amino. diethylaminopropyl)amino. 104...- Phenylamino N-(2-aminocarbonylethyl)- N-(2-aminoearbony1ethyl)N-(3- N-(2-aminoearbonylethyl)-N-(3- Na.

N-(3-diethylamin0 diethylaminopropyl)-amin0. diethylaminopropyD-amino. propyl) amino. 105 "do--. .do.. N-(2-n-butoxycarbonylethyl)-N- N-(2-n-butoxycarbonylethyl)-N- Na (3-diethylau1in0pr0pyl)-amin0. (3-diethylaminopropyl)amino. 106 do do. N-(2-aminoearbonyl-ethyl)-N-(3- N-(2 methylaminocarbonylethyl)-N- Na diethylaminopropyD-amino. (3-diethyleminopropyl)-amino. 107 N-(2-aminocarbonyl- ..do do do..- Na

ethyl)-N-[3-di-(nbutyl)-aminopropyl]- amino. 108 -do -----do N- -aminoearbonylethyl)-N-[3- N-(2aminocarbonylethyl)-N-(3- Na di-(n-butyl)-aminopropyl1-arnino. diethylaminopropyl)-amino. 109--.- Phenylamino Phenylamino N-(2-aminocarbonylethyl)-N-(3- N-(2-dimethylaminocarbonylethyD- Na diethylaminopropyD-amino. N-(3"-diethylaminopropyD-amino. 110 do-.. dodo N-(2-n-buty1aminocarbonylethyl)-N- Na (3 -diethylarninopropyl) -amino. 111 ..do 4-chlorophenyl do N-(2-aminocarbonylethyl)-N-(3- Na diethylaminopropyD-amino. 112 ..do 3-ehl0ropheny1amino dodo Na 113 do 2-methoxyphenylamino ..do do Na Table 3 contains quaternized or protomzed compounds TABLE 3C0nt1m1ed which are made from the stilbene compounds of the presmbene ceding examples 1n accordance with the details of Exam- 5335 ples 6 to 9. They are characterized by the startmg com- MEX? Quaternizing agent (acid M01 pound, the quaternization agent or acid and the number of mols of quaternization agent or acid Which are reacted with 1 mol of starting material.

TABLE 3 Stilbene compound of Ex. Quaternizing agent or acid M01 Dimethylsulphate 2 do 1 Dimethylsulphate 1 1 4-methylbenzene sulphonic acid ethyl ester. 1

2 Diethylsulphate 2 2 Methyl chloride 2 1 2-meth0xyethyl ehloride.. 2 1 2 2 2ethoxyethyl bromide 4 t 2 1 2 Z-n-butoxyethyl chloride 4 3 1 2 2-phenoxyethyl choride 2 4 1 2 2-para-eres0xyethyl chloride 2 1 2 Benzyl chloride 2 13 1 2 Methyl bromide 4 1 2 1-bromo-2-propanol 4 17 1 2 l-chloro-2-propanol-.- 2 28 3 Dimethylsulphate 2 39 3 4-methylbenzenesulphonic acid methyl ester 2 4 Dimethylsulphate 2 41 4 Methyl bromide- 2 41 4 Benzenesulphonie a (1 methyl ester 2 87 4 Methanesulphonie acid methyl ester.- 2 4 -Ldo 4 94 1 4 Ethanesulphonie acid ethyl ester. 4 101 1 4 n-Propyl bromide 4 104 1 Benzyl bromide 2 108 1 Ethyl iodide 2 1 2 10 Dimethylsulphate. 2 20 11 do 2 17 2 7 5 l Formula XV.

2 Last paragraph.

1 7 EXAMPLE OF USE A Production of a softening preparation: 3 parts of the solution, obtained according to the details of Example 6, of the compound of Formula XIV are added to parts of a softener paste containing 75% of distearyldimethylammonium chloride and 25% of isopropanol. Stirring is effected and slow dilution with water under constant stirring until the content of softener is 5%.

20 parts of bleached cotton material in 800 parts of water containing 8 parts of the above softener preparation are treated for minutes at The material is centrifuged without rinsing and subsequently ironed until dry. The resulting material has a soft handle and appears much whiter than a sample treated in the softener bath without any brightener for purposes of comparison.

Instead of distearyl-dimethylammonium chloride it is possible to likewise use other cationic compounds, for example on a basis of l-methyl-l-alkanoylaminoethyl-Z- alkylimidazoliniummethylsulphate or a condensation product of stearic acid and N-p-hydroxyethylethylenediamine in the form of a salt.

EXAMPLE OF USE B A liquor is produced containing 0.5 g. of softener per litre using a softener composition composed of the following constituents Triethanolamine g 5 Dimethylformarnide 'g 10 Distearyl-dimethylammonium chloride g 4 Brightener according to Example 1 mg 160 Example 2 (last paragraph) Example 7 (first compound) (C H5) FN-CHr-CHrCH:

Scale degrees Sample A (brightener of the invention) 80.5 Sample B 69 EXAMPLE OF USE C Bleached cotton cretonne is treated in a bath [5 g./ litre of a washing agent based on a basis of sodium dodecylbenzenesulphonate and 2% of anionic brightener (a triazinyl derivative of 4,4'-diaminostilbene-2,2-disu1- phonic acid) based on the washing agent at a liquor ratio 1:40 during 30 minutes at and rinsing is subsequently effected as in the normal washing operation. To part of the washed cotton material (A) there is added in the last rinsing bath as much of a softener preparation in accordance with Example of Use A, which preparation contains 4% of the brightener described in Example 1 (based on softener), so that the rinsing liquor contains 0.5 g. of softener per litre. Treatment in the cold is effected for 15 minutes (liquor ratio 1:40), centrifuging is efiected and ironing.

The other part of the washed cotton material (B) is treated for purposes of comparison in similar manner in a rinsing bath containing softening agent, but without the addition of the brightener according to the invention. The Samples A and B are compared in daylight. Whereas Sam ple B appears clearly more yellow than before the treatment with the softener, the Sample A appears clearly brighter than the Sample B and also brighter than material which has not been treated in a rinsing bath containing softener.

From the foregoing it is seen that the brightener in accordance with the invention combined with cationic softeners is capable of increasing the whiteness degree of cotton material despite the already present anionic brightener, a result which was in no way to be expected.

Formulae of representative stilbene compounds of the foregoing examples are as follows:

Example 2 (last paragraph) H N-OC-CH -CH,

ll N HgN-OC-CIh-CH,

Example 7 (second compound) Example 8 Example 9 (last paragraph) mc-oc-cm-cm N I Example 136 Example 150 c so;

I I-43 H3O HaC ONHg CHPN/ O SO: e 211000 xwcmcmc ONH;

\ 0, s'ot Example 196 s ot Having thus disclosed the invention what we claim is: 1. A stilbene compound of the formula \l/ S 03MB 403MB \l/ wherein X and Y independently of one another each represents an unsubstituted or substituted phenylamino radical in which the ring substituents may be lower alkyl, lower alkoxy, halogen, cyano, alkylsulphonyl, aminosulphonyl, or acylamino and the N- substituents may be lower alkyl or lower hydroxyalkyl; or a radical of the formula R: --N-(CHz)|-N Rl (II) or of the formula 1 (CHzh-r-Cfi 3- Anton 'N(CHz)$ R (III) R and R independently of one another each represents a hydrogen atom or a low molecular alkylor hydroxyalkyl radical or R and R together with the nitrogen atom represent piperidino, morpholino, pyrrolidino, or hexamethylene imino,

R represents a low molecular alkyl radical which may optionally be substituted with hydroxy, alkoxy, phenoxy, cresoxy, or phenyl,

Me represents an alkali metal, ammonium, or an equivalent of an alkaline earth metal,

Anion represents a colourless anion,

m represents a number from 1 to 3, and

n represents 1 or 2 with the proviso that all radicals R3 (-WEh-x- =4 in the substituents T, X, Y, and Z may be the same or different from one another and all radicals R to R likewise may be the same or dilferent from one another, and the molecule is devoid of a chromophoric radical and, apart from the two sulphonic acid groups attached to the stilbene residue, contains no other anionic water solubilizing group.

2. A stilbene compound according to claim 1 wherein X and Y independently of one another each represents a phenylaminoor methylphenylamino radical or a radical of the formula and T and Z each represents a radical of the Formula VII or of the Formula VIII.

3. A stilbene compound according to claim 2 wherein 23 4. The stilbene compound according to claim 1 of the formula :Na F HgN-OC-CHr-CHrN 5. The stilbene compound according to claim 1 of the formula 0;Na SOaNa mN-oo-om-cm-r r 6. The stilbene compound according to claim 1 of the formula HzN-OC-CHr-CH:

I l-CHICK) O-NH:

7. The stilbene compound according to claim 1 of the formula I I-O CHn-CHz-CO-NH, Da

8. The stilbene compound according to claim 1 of the formula Ih-CHzCHgC ONH,

9. The stilbene compound according to claim 1 of the formula v formula cm I r C I N-CHzCHzC ONH;

l-CHgCHgC ONH,

11. The stilbene compound according to claim 1 of the formula i 211000 N-omomc ONE;

12. The stilbene compound according to claim 1 of the formula 1 13. The stilbenc compound according to claim 1 of the formula mN-oo-cnr-cm N "I l c e l ZCHa-O-SO: N-CHICH1C O-NH,

14. The stilbene compound according to claim 1 of the formula 15. The stilbene compound according to claim 1 of the (D :11: 2 (XIV) '27 1 28 16. The stilbene compound according to claim 1 of the 5 I formula 0. $10. C C x r-cmcmconn, E-QHqQH QONH; a): Hz):

GH;N=(C:H,): Ha-N=( a): e I Q; 17. The stilbene compound according to claim 1 of the formula N @210 ..N J:

o I!1-CH:CH|C ONE;

CaHl

CH|N 0 Cn i4 2 References Cited UNITED STATES PATENTS 3,546,218 12/1970 Tscharner 260240 B 3,600,385 8/1971 Loifelman et a1. 260-240 B U.S. Cl. X.R.

106176; 117-335 T; 252 301.2 W, 543; 26 O239 B, 240.1, 247.2 A, 247.5 B, 249.5, 249.8, 293.87, 326.85, 465.5, 479, 584, 584 R, 260/561